三硝基间苯三酚5-氨基四唑盐的晶体结构及热分解(英文)  

Crystal Structure and Thermal Decomposition of 5-Aminotetrazole Trinitrophloroglucinolate

作　　者：胡晓春[1,2] 张同来[1] 乔小晶[1] 杨利[1] 张建国[1] 崔燕[1,3] 张进[1] 

机构地区：[1]北京理工大学机电工程学院,爆炸科学与技术国家重点实验室,北京100081 [2]防化指挥工程学院三系,北京102205 [3]防化研究院六所,北京102205

出　　处：《物理化学学报》2008年第4期576-580,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(10776002)资助项目

摘　　要：制备得到标题化合物并对其进行了元素分析与红外光谱分析.用X射线衍射方法测得其晶体结构属于正交晶系,空间群Pbca,晶胞参数a=0.6624(2)nm,b=1.7933(4)nm,c=2.3117(5)nm,V=2.7458(9)nm3,Z=4,Dc=1.849g·cm-3.其分子式可写作(ATZ)TNPG·2H2O.5-氨基四唑阳离子(ATZ+)和三硝基间苯三酚阴离子(TNPG-)通过氢键在b轴和c轴方向上联成二维层面,然后在a轴方向通过不同层中的水分子之间的氢键联接起来.用差示扫描量热法(DSC),TG-DTG结合傅立叶变换红外光谱(FT-IR)分析了其热分解过程.在氮气气氛下用10℃·min-1的升温速率测定发现,该化合物经历一个峰温为76℃的吸热过程及一个峰温为203℃的放热过程.前者为脱除结晶水的过程,后者为产物中的TNPG-与ATZ+的热分解过程,放热的焓变为-212.10kJ·mol-1.对该过程估算动力学参数:采用Kissinger法得活化能E=132.1kJ·mol-1,ln(A/s-1)=12.54,r=0.9990;采用Ozawa-Doyle法得E=133.1kJ·mol-1,r=0.9992.5-Aminotetrazole trinitrophloroglucinolate （（ATZ） TNPG） was prepared and characterized by elemental analysis and FT-IR spectroscopy. The crystal structure was determined by X-ray diffraction analysis and it belonged to orthorhombic system and Pbca space group with a=0.6624（2） nm, b=1.7933（4） nm, c=2.3117（5） nm, V=2.7458（9） nm^3, Z=4, and Dc=1.849 g·cm^-3. The molecular formula was confirmed to be （ATZ）TNPG-2H2O. 5-Aminotetrazole cation （ATZ＋） and trinitrophloroglucinol anion （TNPG-） were linked into 2-D layers along b-axis and c-axis by hydrogen bonds. Then the layers were linked along a-axis by hydrogen bonds between the water molecules belonging to different layers. The thermal decomposition mechanism of the compound was studied by differential scanning calorimetry （DSC）, thermogravimetry-thermogravimetric analysis （TG-DTG）, and Fourier transform-infrared （FF-IR） spectroscopy techniques. Under nitrogen atmosphere with a heating rate of 10℃·min^-1, the compound experienced one endothermic process with peak temperature of 76℃ and one exothermal process with peak temperature of 203℃. The former was confirmed to be a dehydrate process. The latter was the decomposition of TNPG-and ATZ^- in the compound. The exothermic enthalpy change of this process was -212.10 kJ· mol^-1. The kinetic parameter calculation from Kissinger＇s method were, E=132.1 kJ· mol^-1, In （A/s^-1）=12.54 with r=-0.9990, and the calculation results from Ozawa-Doyle＇s method were, E=133.1 kJ· mol^-1 with r=0.9992.

关 键 词：三硝基间笨三酚 5-氨基四唑 TNPG 制备 晶体结构 热分解 

分 类 号：O621.2[理学—有机化学]